Tunable materials

ABSTRACT

A corrosion resistant material is described including a substrate, a first material including less than about 90% of an amino group or epoxy group, between about 0.05% and about 50% siloxane, between about 5% and about 80% nanoparticles, microparticles, or macroparticles, and between about 0.1% and about 5% of a first functionalized graphitic material, a second material including less than about 90% of a silyl group, between about 0.05% and about 50% siloxane, between about 5% and about 80% nanoparticles, microparticles, or macroparticles, and between about 0.1% and about 5% of a second functionalized graphitic material, and a third material including less than about 90% of an amino group or epoxy group and a silyl group, between about 0.05% and about 50% siloxane, between about 5% and about 80% nanoparticles, microparticles, or macroparticles, and between about 0.1% and about 5% of a third functionalized graphitic material.

This application is a continuation of U.S. Ser. No. 16/028,925, filedJul. 6, 2018, now U.S. Pat. No. 10,323,152, which is a divisionalapplication of U.S. Ser. No. 15/605,663, filed May 25, 2017, now U.S.Pat. No. 10,017,649, which is a continuation application of U.S. Ser.No. 14/410,009, filed Dec. 19, 2014, now U.S. Pat. No. 9,725,603, whichis a 371 national stage entry of PCT/US2013/038852, filed Apr. 30, 2013,which claims priority to U.S. Ser. No. 61/850,861, entitled TUNABLEMATERIALS, filed Feb. 20, 2013, and Finland Serial No. 201201980993,entitled TUNABLE MATERIALS, filed Jun. 21, 2012.

BACKGROUND

Composites may be fabricated with thermoset plastics such as epoxies,polyurethanes, and silicones. Epoxies may be produced by reacting anepoxy resin and a hardener. Polyurethane polymers can be formed byreacting an isocyanate with a polyol. Silicones may comprise polymerizedsiloxanes with organic side groups.

Carbon nanotubes (CNTs) and graphene have been used to reinforcethermoset plastics like epoxies, polyurethanes, silicones, and otherresins and polymers. CNTs, functionalized CNTs (or hybrid CNTs, denotedHNTs), graphene, and functionalized graphene may collectively bereferred to as hybrid graphitic materials (HGMs). These HGMs can beincorporated into any of the epoxy components such as the epoxy resinand hardener. HGMs may also be incorporated into polyurethanes andsilicones.

Thermoset plastics, CNTs, graphene, and HNTs may increase modules andtoughness, but elasticity may be preferred for certain plasticcomposites. In order to increase elasticity, siloxane may be added.Siloxane backbone may be coiled, and it can be covered by alkyl or arylgroups in silicones. Thus, silicones can be very flexible andhydrophobic. Hydrophobicity can be increased by functionalization withgroups such as fluorinated alkyl or aryl groups.

Numerous functionalization methods for the CNTs have been developed.These include nitric acid/sulfuric acid oxidation of the CNTs, arylradical addition to the CNTs, ball milling induces addition of aminesand sulfides into the CNTs, butyl lithium activated coupling to alkylhalides, and ultrasonic vibration assisted addition of many reagents,including amines, and epoxies. Improving mechanochemical reactions, suchas mechanical or ultrasound cutting, may induce chemical reactions ofthe CNTs.

An anticorrosive coating may contain sacrificial metal particles, suchas zinc particles. The concentration of the particles may exceed thepercolation limit, which is about 30% for spherical particles. Highconcentration of these particles can reduce the integrity of thecoating, especially if the particles are not chemically bound with thepolymer. Anticorrosive coatings may use sacrificial metal particles thatare electrically connected with a coated metal surface through a CNT orgraphene network. Using the CNT or graphene network may require lesssacrificial metal particles within an anticorrosive coating.Additionally, the graphitic material may be coated with a metal layer.The metal layer may be comprised of nanoparticles or microparticles. Themetal particles may be coated with a thin oxide layer unless thegraphitic material is coated in the absence of oxygen. With thenanoparticles, the oxide layer can be a relatively large part of theparticle. The oxide layer may also be a large portion for a metalcoating around a CNT. Besides metallic particles, the particles may alsobe ceramic.

SUMMARY

This Summary is provided to introduce a selection of concepts in asimplified form that are further described below in the DetailedDescription. This Summary is not intended to identify key factors oressential features of the claimed subject matter, nor is it intended tobe used to limit the scope of the claimed subject matter.

In one implementation, a method of modifying a graphitic materialcomprising the steps of: 1) providing a graphitic material; 2) providinga first molecule comprising a first group, a spacer, and a second group;3) providing a second molecule comprising a third group, a spacer, and afourth group, wherein said third group is a different group from saidfirst group; and 4) bonding the first molecule and the second moleculeto the graphitic material.

To the accomplishment of the foregoing and related ends, the followingdescription and annexed drawings set forth certain illustrative aspectsand implementations. These are indicative of but a few of the variousways in which one or more aspects may be employed. Other aspects,advantages and novel features of the disclosure will become apparentfrom the following detailed description when considered in conjunctionwith the annexed drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

What is disclosed herein may take physical form in certain parts andarrangement of parts, and will be described in detail in thisspecification and illustrated in the accompanying drawings which form apart hereof and wherein:

FIG. 1 is a plain view of the process disclosed herein.

FIG. 2 schematically illustrates what is disclosed herein.

FIG. 3 schematically illustrates what is disclosed herein.

FIG. 4 schematically illustrates what is disclosed herein

FIG. 5 schematically illustrates what is disclosed herein.

FIG. 6 schematically illustrates what is disclosed herein.

FIG. 7 schematically illustrates what is disclosed herein.

FIG. 8 schematically illustrates what is disclosed herein.

FIG. 9 schematically illustrates what is disclosed herein.

FIG. 10 schematically illustrates what is disclosed herein.

DETAILED DESCRIPTION

The claimed subject matter is now described with reference to thedrawings, wherein like reference numerals are generally used to refer tolike elements throughout. In the following description, for purposes ofexplanation, numerous specific details are set forth in order to providea thorough understanding of the claimed subject matter. It may beevident, however, that the claimed subject matter may be practicedwithout these specific details. In other instances, structures anddevices are shown in block diagram form in order to facilitatedescribing the claimed subject matter.

The word “exemplary” is used herein to mean serving as an example,instance or illustration. Any aspect or design described herein as“exemplary” is not necessarily to be construed as advantageous overother aspects or designs. Rather, use of the word exemplary is intendedto present concepts in a concrete fashion. As used in this application,the term “or” is intended to mean an inclusive “or” rather than anexclusive “or.” That is, unless specified otherwise, or clear fromcontext, “X employs A or B” is intended to mean any of the naturalinclusive permutations. That is, if X employs A; X employs B; or Xemploys both A and B, then “X employs A or B” is satisfied under any ofthe foregoing instances. Further, at least one of A and B and/or thelike generally means A or B or both A and B. In addition, the articles“a” and “an” as used in this application and the appended claims maygenerally be construed to mean “one or more” unless specified otherwiseor clear from context to be directed to a singular form.

Although the subject matter has been described in language specific tostructural features and/or methodological acts, it is to be understoodthat the subject matter defined in the appended claims is notnecessarily limited to the specific features or acts described above.Rather, the specific features and acts described above are disclosed asexample forms of implementing the claims. Of course, those skilled inthe art will recognize many modifications may be made to thisconfiguration without departing from the scope or spirit of the claimedsubject matter.

Also, although the disclosure has been shown and described with respectto one or more implementations, equivalent alterations and modificationswill occur to others skilled in the art based upon a reading andunderstanding of this specification and the annexed drawings. Thedisclosure includes all such modifications and alterations and islimited only by the scope of the following claims. In particular regardto the various functions performed by the above described components(e.g., elements, resources, etc.), the terms used to describe suchcomponents are intended to correspond, unless otherwise indicated, toany component which performs the specified function of the describedcomponent (e.g., that is functionally equivalent), even though notstructurally equivalent to the disclosed structure which performs thefunction in the herein illustrated exemplary implementations of thedisclosure.

In addition, while a particular feature of the disclosure may have beendisclosed with respect to only one of several implementations, suchfeature may be combined with one or more other features of the otherimplementations as may be desired and advantageous for any given orparticular application. Furthermore, to the extent that the terms“includes,” “having,” “has,” “with,” or variants thereof are used ineither the detailed description or the claims, such terms are intendedto be inclusive in a manner similar to the term “comprising.”

Both carbon nanotubes (also referred to as CNTs) and graphene aregraphitic materials.

They are substances composed essentially of pure carbon. The edges ofthe CNTs and graphene may have other elements, such as hydrogen andoxygen. Graphene may have atoms arranged in a regular hexangular patternsimilar to graphite, but in one-atom fixed sheet. Graphene may becomprised of carbon atoms, where each carbon atom is bonded with threeother carbon atoms. The carbon atom may form four covalent bonds, whereeach carbon has both a single and double bond. These covalent bonds canprovide strength within the graphene material. It can be very light inweight, but can provide strength as a material. Even with smallquantities of graphitic materials added to a composite, the tensilestrength of the composite may be increased. In addition to theirstrength, graphitic materials are also known for their electronicconductance.

Generally, graphitic materials may be smooth and regularly shaped, butmay slip easily within the nanocomposite. Slipping may be prevented byfunctionalizing graphitic materials. Proper functionalization can allowcovalent, coordination, or ionic bond formation between functionalizedgraphitic material, various particles, polymers, and the surface to beprotected by the coating.

Graphene can be fabricated in two different ways, either from smallerbuilding blocks (bottom-up), or exfoliating graphite (top-down).Bottom-up method allows fabrication of continuous graphene layers on asubstrate. That is ideal method for the fabrication of transistors andelectronic circuits. For large scale materials fabrication, exfoliationof graphite can be a more suitable approach. Exfoliating can be done byseparating graphene layers by intercalating hydrogen or some other atomsor ions into graphite, or by ultrasonic vibration. The edge of graphenesheet contains other atoms than carbon, for example, hydrogen or oxygen.The edge can be functionalized deliberately by any functional group.

Carbon nanotubes are also a graphitic material but with a cylindricalstructure. Each CNT is a molecule with a certain structure which may ormay not be exactly known. CNTs can be durable, and they can resistnanocracking due to thermal expansion and other contraction cycles whenused in composites or coatings. Carbon nanotubes may have a high tensilestrength compared to many other materials. They may also increase thetensile strength of composites, even when they are added to thecomposites in small quantities. In addition, CNTs may have an increasedpersistence length. Persistence length is a mechanical propertymeasurement quantifying the stiffness of a polymer. Most polymers canhave a persistence length of about 1 nm to about 2 nm. However,multiwalled carbon nanotubes (MWNTs) can have persistence length morethan about 100 nm. Single-walled carbon nanotubes (SWNTs) anddouble-walled carbon nanotubes (DWNTs) may have an increased persistencelength as well. Both the high tensile strength and persistence lengthcan allow graphitic materials to provide tensile strength fornanocomposites, especially if they may be chemically bonded with apolymer or particles that can be part of the composition describedherein.

Functionalized CNTs may be fundamentally different than the CNTs thatmay be used as a starting material. Functionalized CNTs may also bedifferent than CNTs that have not been functionalized. FunctionalizedCNTs may be molecules that can have different chemical structures,chemical, and physical properties than CNTs. For comparison, celluloseand functionalized celluloses, such as carboxymethyl cellulose (CMC),may have different properties. CMC may be chemically derived fromcellulose, but it may not function like cellulose. CMC has totallydifferent chemical and physical properties.

FIG. 1 provides a process of modifying graphitic material, comprisingthe steps of: 1) providing a graphitic material; 2) providing a firstmolecule comprising a first group, a spacer, and a second group; 3)providing a second molecule comprising a third group, a spacer, and afourth group, wherein said third group is a different group from saidfirst group; and 4) bonding the first molecule and the second moleculeto the graphitic material. Within the process, the first group maycomprise at least one group of hydroxyl, thiol, amino, epoxy, carboxyl,and silyl, and the second group may comprise at least one group ofamino, epoxy, hydroxyl, carboxyl, silyl, and thiol. Also within theprocess described herein, the third group may comprise at least onegroup of thiol, carboxyl, trialkoxysilyl, phosphoryl ester, crown ether,cryptand, dioxime, and N-heterocycle, and the fourth group may compriseat least one group of amino, epoxy, hydroxyl, carboxyl, silyl, andthiol. The first group may be different than the third group within thegraphitic material. The first molecule may be bound to the graphiticmaterial before the second molecule, or the second molecule may be boundto the graphitic material before the first molecule. Additionally, thefirst molecule comprising a first group, a spacer, and a second groupmay bound simultaneously with the second molecule comprising a thirdgroup, a spacer, and a fourth group, as described in the method above.The first molecule may comprise at least one molecule of diaminocompound, diepoxy compound, and amino alcohol compound. The secondmolecule may comprise at least one molecule of a diester ofO-phosphorylethanolamine and aminopropyl trialkoxysilane.

Within the method shown in FIG. 1, the graphitic material can befunctionalized. The graphitic material may be at least one graphiticmaterial of graphene and CNTs. For FIG. 1, a CNT 101 may be depicted asthe graphitic material.

The first group 102 (denoted as Y) may be comprised of at least onegroup of hydroxyl, thiol, amino, epoxy, carboxyl, and silyl. Examples ofthe first group 102 for silyl may include, but are not limited to,dimethylsilyl, and diphenylsilyl.

The third group 103 (denoted as W) may be comprised of at least onegroup of thiol, carboxyl, trialkoxysilyl, phosphoryl ester, crown ether,cyclopetadienyl, cryptand, dioxime, and N-heterocycle. Examples of thethird group 103 may include, but are not limited to, phosphoryldi(trichloroethyl) ester, phosphoryl di(cyanoethyl) esters, 18-crown-6,2,2,2-cryptand, 2,1,1-cryptand, dimethylglyoxime, and phenantrolinyl.For specific metals, cyclopentadienyl may bind to iron, imidazolyl maybind to iron, 18-crown-6 may bind to magnesium, 2,2,2-cryptand may bindto zinc, imidazolyl may bind to zinc, 2,1,1-cryptand may bind tomagnesium, dimethylglyoxime may bind to nickel, imidazolyl may bind tocopper, and phenantrolinyl may bind to copper. Several other ligandswell known in the art may also be used.

The second group 104 (denoted as Z) and fourth group 105 (denoted as X)comprises at least one group of amino, epoxy, hydroxyl, carboxyl, silyl,and thiol. Examples of the second group 104 and fourth group 105 forsilyl may include, but are not limited to, dimethylsilyl anddiphethylsilyl.

Within the first molecule, a spacer 106 may be bound between the firstgroup 102 (denoted as Y) and the second group 104 (denoted as Z). Thespacer 106 of the first molecule may vary. The spacer may be differentfor the first molecule and second molecule. For example, the spacer maybe a propylene spacer, as shown in FIG. 1. The spacer 106 may be lessthan about 1 nm. The length of the spacer 106 may still allow forelectron tunneling when the spacer 106 is less than about 1 nm. Also,the first group Y 102, third group W 103, or both the first group Y 102and third group W 103 may be bound to the spacer 106 such that the firstgroup Y 102, third group W 103, or both the first group Y 102 and thirdgroup W 103 may be in contact with the CNT 101.

The spacer 107 of the second molecule may also vary. Within the secondmolecule, a spacer 107 may be bound between the third group 103 (denotedas W) and the fourth group 105 (denoted as X). For example, the spacermay be a propylene spacer, as shown in FIG. 1. The spacer 107 may beless than about 1 nm. The length of the spacer 107 may also still allowfor electron tunneling when the spacer 107 is less than about 1 nm.Also, the first group Y 102, third group W 103, or both the first groupY 102 and third group W 103 may be bound to the spacer 107 such that thefirst group Y 102, third group W 103, or both the first group Y 102 andthird group W 103 may be in contact with the CNT 101.

Further, polymerizing may occur onto the first group Y 102.Polymerization may also occur onto the third group W 103 unless thirdgroup W 103 may be a specific metal binding ligand. Polymerization mayinclude a polyurethane, an epoxy, or a silicone. A sacrificial metalparticle may be bound to the third group W 103. The sacrificial metalparticle may comprise at least one metal of zinc, magnesium, nickel,aluminum, and cobalt. Within the methods described herein, thesacrificial metal particle may be in electrical contact with thegraphitic material. Within the electrical contact, the spacer may beless than about 1 nm in length, and electron tunneling may occur.

The method described herein in FIG. 1 may allow at least two differenttypes of molecules to be bound to a graphitic material. Bonding may beprovided by at least one method of mechanical milling, ultrasonicvibration, and high pressure microfluidic injection. Instead ofproviding a mixture of graphitic materials where only one type ofmolecule may be bound to a graphitic material, the method describedherein may permit a single functionalized graphitic material to be used.The amount and ratio of binding for both the first and second moleculesmay be tailored for a specific application.

The functionalized graphitic material may also be incorporated into aplastic composite. The plastic composite may be thermoset. The plasticcomposite comprises at least one resin of epoxy, polyacrylate,polyurethane, and phenolformaldehyde. The plastic composite may be atunable material composition. The tunable material may comprise: 1) athermoset plastic; and 2) a graphitic material prepared by the methodcomprising the steps of: a) providing a graphitic material; b) providinga first molecule comprising a first group, a spacer, and a second group;c) providing a second molecule comprising a third group, a spacer, and afourth group, wherein said third group is a different group from saidfirst group; and d) bonding the first molecule and the second moleculeto the graphitic material. Within the process for providing a firstmolecule, the first group may comprise at least one group of hydroxyl,thiol, amino, epoxy, carboxyl, and silyl, and the second group maycomprise at least one group of amino, epoxy, hydroxyl, carboxyl, silyl,and thiol. Also within the process described herein for providing asecond molecule, the third group may comprise at least one group ofthiol, carboxyl, trialkoxysilyl, phosphoryl ester, crown ether,cryptand, dioxime, and N-heterocycle, and the fourth group may compriseat least one group of amino, epoxy, hydroxyl, carboxyl, silyl, andthiol. The first group may be different than the third group within thegraphitic material. The tunable material composition can be used inanticorrosive coatings in electromagnetic interference shields, magneticshields, conductors, super capacitors, pre-impregnated composites,epoxies, polyacrylates, and polyurethanes. The composition may alsocomprise a silicone.

Within the composition described above, the thermoset plastic may be atleast one plastic of an epoxy, polyacrylates, polyurethane, andphenolformaldehyde. The graphitic material may be at least one carbon ofcarbon nanotubes and graphene. Further, the graphitic material can befunctionalized. The graphitic material can be functionalized with atleast one hardener of diaminobenzene, diamino polyethyleneoxide, diaminopolypropyleneoxide, diamine cyclohexane derivatives, and aminated talloil. The graphitic material may be functionalized in the absence ofoxygen and water.

The composition described above may further comprise at least oneparticle of macroparticles, microparticles, and nanoparticles. Themacroparticles can comprise at least one macroparticle of sand, glass,basalt, alumina, silica, titanium dioxide, ceramic, and graphite fibers.The microparticles comprise at least one microparticle of titaniumdioxide, silica, ceramic, graphite, iron phosphate, alumina, nickel,cobalt, zinc, aluminum, and magnesium. The nanoparticles comprise atleast one nanoparticle of titanium dioxide, copper oxide, ironphosphate, silver, silica, and alumina.

FIG. 2 also provides an embodiment of the method described herein for aprocess of modifying graphitic carbon, comprising the steps of: 1)providing a graphitic material; 2) providing a first molecule comprisinga first amino group, a spacer, and a trialkoxysiloxane group; 3)providing a second molecule comprising a second amino group, a spacer,and a third amino group; and 4) bonding the first amino group and thesecond amino group to the graphitic material. Alternatively, the methodof FIG. 2 described herein may be a process of modifying graphiticcarbon, comprising the steps of: 1) providing a graphitic material; 2)providing a first molecule comprising a second amino group, a spacer,and a third amino group; 3) providing a second molecule comprising afirst amino group, a spacer, and a trialkoxysiloxane group; and 4)bonding the first amino group and the second amino to the graphiticmaterial. Additionally, the molecule may comprise a first amino group, aspacer, and a trialkoxysiloxane group may be added simultaneously withthe molecule comprising a second amino group, a spacer, and a thirdamino group, both described in the two methods above. The first moleculemay be bound to the graphitic material before the second molecule, orthe second molecule may be bound to the graphitic material before thefirst molecule. Additionally, the first molecule comprising a firstgroup, a spacer, and a second group may be bound simultaneously with thesecond molecule comprising a third group, a spacer, and a fourth group,as described in the method above. Bonding may be provided by at leastone method of mechanical milling, ultrasonic vibration, and highpressure microfluidic injection.

Within the method shown in FIG. 2, the graphitic material can befunctionalized. The graphitic material may be at least one graphiticmaterial of graphene and CNTs. For FIG. 2, a CNT 201 may be depicted asthe graphitic material.

The top illustration in FIG. 2 provides the introduction of both theamino group 202 and the trialkoxysiloxane group 203 to the CNT 201.Within the method, both the amino group 202 and the trialkoxysiloxanegroup 203 may then be bonded to the CNT 201 with a spacer (206 and 207),as shown in the bottom illustration in FIG. 2. Specifically, the diaminocompound may bind through the amine group 204 to the CNT 201 to form asecondary amino group 208. Similarly, the second molecule may also bindthrough the amine group 205 to the CNT 201 to form a secondary aminogroup 209.

The spacer portion of the molecule may vary. For example, the spacer maybe a propylene spacer, as shown in FIG. 2. The spacer may be differentfor the first molecule and second molecule. The binding of both theamino group 202 and trialkoxysiloxane group 203 may occur due to thefunctionalization of an amino group with both the amino group 202 andtrialkoxysiloxane group 203. The amino group may be bound directly tothe CNT 201, allowing both the amino group 202 and trialkoxysiloxanegroup 203 to then functionalize the CNT 201.

The amino group 202 may then provide a starting point for further epoxyand urethane functionalities, and the both trialkoxysiloxane group 203may provide a starting point of silicone functionalities. The epoxy andurethane functionalities as well as other amino functionalities mayprovide a rigidity and toughness to the CNT 201, while the siliconefunctionalities may provide a softness and flexibility to the CNT 201.Together, the multiple functionalities within the CNT 201 may providedesired properties and also a means to tailor the properties to aspecific application. For example, an amino group may be polymerizedwith an epoxy monomer, epoxy oligomer, urethane monomer, or urethaneoligomer. Also, the trialkoxysiloxane group may be polymerized withsilicone monomer or oligomer.

The graphitic material may be functionalized with at least one hardenerof diaminobenzene, diamino polypropyleneoxide, diamine cyclohexanederivatives, and aminated tall oil. The graphitic material may also befunctionalized with another curing agent. The graphitic material mayalso be functionalized in the absence of oxygen and water.

FIG. 3 shows various versions of functionalizing CNTs with polymers. Apolymer may be connected through a primary or secondary amino group,hydroxyl group, or epoxy group. The hydroxyl group may include aphenolic hydroxyl group. These functionalities may serve as startingpoints for polyurethane, polyacrylate, polyurea, epoxy resin,phenol-formaldehyde resin, polyacrylates, or other polymers. Oneembodiment of the general principle of the method described herein is aCNT, or graphene sheet that is functionalized with alkoxysilane, oramino functionalities, or simultaneously with both of these.

Each functionalized CNT or graphene sheet may contain tens or hundredsof functional groups being able to bind each particle multiple times.Each functionalized CNT or graphene sheet may also bind multipleparticles. Similarly, each functionalized CNT or graphene sheet may bindmultiple polymer chains. These functionalities may be directly connectedwith CNTs or graphene, or spacers may be used. Spacers may containaliphatic, aromatic or heterocyclic moieties.

In FIG. 3A, the CNT 301 may be functionalized with only thetrialkoxysiloxane group 304. If only the trialkoxysiloxane group 304 maybe used, then only silicone functionalities may be bound. In FIG. 3B,the CNT 302 may be functionalized with only the amino group 305. If onlythe amino group 305 may be used, then only epoxy, urethane, and otheramino functionalities may be bound. Although a mixture of thefunctionalized CNT 301 and CNT 302 may be used in an application,neither provides both the amino group 305 and trialkoxysiloxane group304 within a single CNT or other graphitic material. FIG. 3C shows themethod described herein, where the CNT 303 may be functionalized withboth the amino group 305 and the trialkoxysiloxane group 304.

FIG. 4 may illustrate how side chains may be grown onto the graphiticmaterial. In the beginning of the reaction shown at the top of FIG. 4,the CNT 401 may contain both the amino group and trialkoxysiloxane groupbound to it. In this example, the silicone 403 may be reacted in thepresence of a catalytic amount of water. The reaction illustrated inFIG. 4 may allow for later polymerization of epoxy 402 and silicone 403,but polyurethane may also be polymerized in place of epoxy 402. Fromthis reaction, both the epoxy functionality 405 and the siliconefunctionality 404 may then provide different properties to the CNT 401.

FIG. 5 may provide three different pictorial representations of how thechains may be grown onto the graphitic material. In this figure, thegraphitic material can be the CNT 501. In FIG. 5A, the CNT 501 may havemultiple silicone group side chains 504. In FIG. 5B, the CNT 502 mayhave multiple epoxy or polyurethane side chains 505. FIG. 5C providesthe CNT 503 which may comprise both epoxy or polyurethane side chains505 and silicone group side chains 504. In general, these various sidechains can be grafted onto the CNT. The side chains may be branched. Ifthe polymer chains are sufficiently different physically, chemically, orboth physically and chemically, such as in FIG. 5C, the CNT 503 mayseparate and form layered structure, as further described in FIG. 6.These layers may be weakly bound, or strongly bound, if a biphasic CNTis included into a composition. This kind of biphasic CNT may contain atleast two types of branches that are able to interact strongly with bothlayers, potentially allowing the fabrication of self-stratifyingcoatings.

Described herein in FIG. 5C can allow for the combination of both hardand soft plastic composites and coating materials with functionalizedCNTs. The plastic composites may be thermoset. The plastic compositesmay include epoxies, polyurethanes, polyacrylates, andphenolformaldehyde. These coatings can be impact and crack resistant.Although abrasion resistance may be acceptable, it may be improved bycovalently linking nanoparticles or microparticles.

In FIG. 6, multiple layers of CNTs may be demonstrated. The CNTs (601,602, and 603) are provided within the figure. The separate layers offunctionalized CNTs, labeled as 608 and 610 within the figure, may be asa result of the stratification of the functionalized CNTs. Anintermediate area 609 may be located within the separate CNT layers of608 and 610. The intermediate layer 609 may be used to bind the separatefunctionalized CNT layers 608 and 610 together. The layers may form whensilicone layer 608 separates from the epoxy layer 610. Namely, themethyl groups within the silicone may provide layers. However, thephenyl groups within the silicone may prevent layers from formingespecially if phenyl groups have polar substituents, such as methoxy.There may be only methyl groups within the silicone or only phenylgroups within the silicone. There may also be both methyl and phenylgroups within the silicone. If the layers may be formed, they may be asthin as about 10 nm. The layers may also be about 50 nm to about 50 μm.

The degree of the functionalization of carbon nanotubes can be adjustedin a wide range of moieties covalently bound per micrometer of a carbonnanotube. For example, the functionalities may be amino groups that caninitiate the polymerization of an epoxy compound. The functionalitiesmay also be amino groups that can initiate the polymerization of apolyurethane compound. The functionalities may be trialkoxysiloxanegroups that can initiate the polymerization of a silicone.

Within the layers, there may be interaction between the amino group sidechains 605, 607 and trialkoxysiloxane group side chains 604 and 606.Because of these interactions, there may be binding and crosslinkingbetween the functionalized CNTs.

The layered structure provided in FIG. 6 may allow for coatings thatresist cracking since they can be less rigid because of the siliconegroups. The layered structure may also assist in applications in which alayered structure may be advantageous. For instance, these layeredstructures may be used in ship coatings in which barnacles may peel offat least one layer of the coating at a time, but the layered structurecan remain within coating. Aromatic or aliphatic curing agents may alsobe used within the layered structure.

The functionalized graphitic material may be bound with a polymer, ametal particle, or both. The method described herein may allow moreelectrical conduction than a mere mixing of components. If electricalcontact between a particle and graphitic material is desired, the spacermay be short.

FIG. 7 may provide one embodiment of a structural representation of atunable coating or plastic composite. Anticorrosive coatings may be anapplication of the process described herein. The tunable materialcomposition in FIG. 7 may comprise: 1) a thermoset plastic; 2) silicone;and 3) at least one functionalized graphitic material of carbonnanotubes and graphene prepared by the method comprising the stepsof: 1) providing a graphitic material; 2) providing a first moleculecomprising a first amino group, a spacer, and a trialkoxysiloxane group;3) providing a second molecule comprising a second amino group, aspacer, and a third amino group; and 4) bonding the first amino groupand the second amino to the graphitic material. Alternatively, themethod of providing at least one functionalized graphitic material maybe prepared by other methods described above in FIG. 2. The firstmolecule may be bound to the graphitic material before the secondmolecule, or the second molecule may be bound to the graphitic materialbefore the first molecule. Additionally, the first molecule comprising afirst amino group, a spacer, and a trialkoxysiloxane group may boundsimultaneously with the second molecule comprising a second amino group,a spacer, and a third amino group, as described in the method above.

FIG. 7 may depict the molecular connections for the methods describedherein. The elastic polymer 704 may be depicted as a spring (previouslydepicted as circles in FIG. 5A). The elastic polymer 704 may includesiloxane functionalities. The more rigid polymer 705 may be shown astriangles in FIG. 7. The more rigid polymer 705 may include epoxy,polyurethane, polyacrylates, and phenolformaldehyde. The three types offunctionalized CNTs 701, 702, and 703 may correspond to 501, 502, and503 in FIG. 5. Polymer chains, including the elastic polymer 704 and themore rigid polymer 705, can form a bridge between two functionalizedCNTs, or bind functionalized CNT with a particle 706 and 707. Particles706 and 707 may be bound with functionalized CNTs through a shortspacer. Arrows depict the binding of polymers (704 and 705) orfunctionalized CNTs (701, 702, and 703) with the particles (706 and 707)or substrate 709. Polymer chains may be cross-linked. If polymerizationreactions are orthogonal, no block polymers or graft polymers may beformed.

The present description can further provide a method to preparecoatings. This method may comprise the steps of: 1) functionalizing CNTsor graphene with amine hardener, aminopropyl trimethoxysilane,macroparticles, microparticles, or nanoparticles, 2) mixing thefunctionalized CNT with epoxy to form a mixture, 3) coating the moldwith the mixture, 4) injecting the bulk epoxy mixture into the mold, and4) curing the mixture.

Siloxane 704 segments within FIG. 7 can be formed from monomers, or theycan be oligomers which may be partially prepolymerized. These componentscan be mixed with hardener or epoxy or both. Suitable monomers mayinclude di(methoxyphenyl), dimethoxysilane, dianisyl dimethoxysilane,dimethyl dimethoxysilane, diphenyl diethoxysilane, aminopropyltrimethoxysilane (also known as APTMS), and tetraethoxysilicate (alsoknown as TES). However, monomers may also include almost any aliphaticor aromatic moiety as well as some of their functionalized forms, suchas chlorinated and fluorinated derivatives. These monomers may bepolymerized if there may be a catalytic amount of water present. APTMSand TES may provide branching points in siloxane chain. APTMS can, inaddition, serve as both a starting and end point for siloxanepolymerization. Too many covalent epoxy contacts may reduce or eliminatethe elasticity of siloxane, and the concentration of free APTMS where itmay not be bound to functionalized CNT's or nanoparticles, may be lessthan about 10% of all silane components. Another kind of siliconepolymer may be formed, for example, from vinyl dimethylsilane in thepresence of catalytic amount of platinum. By varying side groups, manyother analogous monomers can be used. In order to provide a startingpoint in a functionalized carbon nanotube, aminopropyl dimethylsilanemay be used. The end point may be functionalized with aminopropyl vinylmethylsilane. Several analogous molecules could be used instead of theseexamples. Additionally, an amino group may serve as both a starting andend point for epoxy polymerization.

Within a composition comprising graphitic material and metal particle,the electrical contact between the metal particle and the graphiticmaterial may be weak. This weakness may be due to layer of polymerwrapped around the metal particle, the graphitic material, or both ofthem. The method described herein may increase the electrical contactand can also provide the mechanism for chemical contact between metalparticles and polymer. By incorporating functionalized graphiticmaterials, a stronger electrical connection may exist between the metalparticle and the metal substrate. The metal particles may benanoparticles or microparticles. Within the method described herein, theorthogonal chemistries may assist in the attachment of metal particlesand polymers with the graphitic material through covalent bonding.Orthogonal chemistries may not interfere with each other. The orthogonalchemistries may happen at ambient conditions. However, orthogonalchemistries may also use UV, IR, or some other curing method.

FIG. 8 may provide a means in which to bind ceramic or metallicparticles to the functionalized graphitic material. Besides polymericbinding described above, single particles may also be bound. In FIG. 8,the CNT 801 may be shown. Both silica (SiO₂) 802 and aluminum oxide(Al₂O₃) 803 may be bound to the CNT 801 through the trialkoxysiloxanegroup. Trimethoxysilane groups may also be able to bind silica oraluminum oxide. Further, a sacrificial metal particle may be bound tothe trialkoxysiloxane group. The sacrificial metal particle may compriseat least one metal of zinc, magnesium, nickel, aluminum, and cobalt.Within the methods described herein, the sacrificial metal particle maybe in electrical contact with the graphitic material. Within theelectrical contact, the spacer may be less than about 1 nm in length,and electron tunneling may occur between the CNT 801 and a metallicparticle.

The method described herein may provide a means to avoid passivation ofsacrificial particles. Most binding groups (for example, the third group103 in FIG. 1) may not be bound by sacrificial particles. If thedistance between these groups is about 0.4 nm to about 2 nm on theaverage, then transfer of metal cations may be possible through ionicconductance. With ionic conductance, sacrificial metal cations may beremoved from the surface of the particle after oxidative reaction, andthe active metal surface may then be exposed. The third groups (shown as103 in FIG. 1) may be selective for the sacrificial metal cations. Thismethod may allow electronic and ionic conductance along functionalizedgraphitic material. However, a high degree of functionalization maydecrease the electric conductance, especially if single-walled CNTs areused. The effect may be less for double-walled CNTs and multi-walledCNTs. The density of ligands may be smaller if polymeric ionicconductors are attached with graphitic material. Nonlimiting examples ofpolymeric ionic conductors may be diamino polyethylene oxide,polyallylamine, and polypyrrolidine.

FIG. 9 may provide a pictorial view one embodiment of the tunablematerial 801 as described herein. The tunable material composition maycomprise: 1) a thermoset plastic; 2) silicone; and 3) at least onefunctionalized graphitic material of carbon nanotubes and grapheneprepared by the method comprising the steps of: 1) providing a graphiticmaterial; 2) providing a first molecule comprising a first amino group,a spacer, and a trialkoxysiloxane group; 3) providing a second moleculecomprising a second amino group, a spacer, and a third amino group; and4) bonding the first amino group and the second amino to the graphiticmaterial. Alternatively, the method of providing at least onefunctionalized graphitic material may be prepared by other methodsdescribed above in FIG. 2. The first molecule comprising a first aminogroup, a spacer, and a trialkoxysiloxane group may be bound to thegraphitic material before the second molecule comprising a second aminogroup, a spacer, and a third amino group, or the second molecule may bebound to the graphitic material before the first molecule. Additionally,the first molecule comprising a first amino group, a spacer, and atrialkoxysiloxane group may bound simultaneously with the secondmolecule comprising a second amino group, a spacer, and a third aminogroup, as described in the method above. Also, combinations of the abovemethods may also be used. As also described in FIG. 7, other materialsmay be included within the composition in FIG. 7. The tunable material901 may also contain at least one particle of macroparticles 902,microparticles 903, and nanoparticles 904; a thermoset plastic;silicone; at least one graphitic material of carbon nanotubes andgraphene; and a means for providing at least one graphitic material ofcarbon nanotubes and graphene by high pressure hydrodynamic injection.

Within the tunable material 901 in FIG. 9, macroparticles 902,microparticles 903, and nanoparticles 904 may be dispersed through thethermoset plastic 905. The thermoset plastic may include at least oneplastic of an epoxy, a polyurethane, a polyacrylate, and aphenolformaldehyde. In FIG. 9, at least one particle of macroparticles902, microparticles 903, and nanoparticles 904 may be added.Macroparticles 902 may dimension between about 100 μm to about 2 mm.Microparticles 903 may be about 200 nm to about 100 μm. Nanoparticles904 may be about 1 nm to about 200 nm. The macroparticles 902 maycomprise at least one macroparticle of sand, glass, basalt, alumina,silica, titanium dioxide, ceramic, graphite fibers, and other metalparticles. The microparticles 903 may comprise at least onemicroparticle of titanium dioxide, silica, ceramic, graphite, ironphosphate, alumina, nickel, cobalt, zinc, aluminum, magnesium, and othermetal particles. The nanoparticles 904 may comprise at least onenanoparticle of titanium dioxide, copper oxide, iron phosphate, silver,silica, alumina, and other metal particles. The macroparticles 902,microparticles 903, and nanoparticles 904 may also provide desiredcharacteristics to the tunable material 901, depending on theapplication. For example, titanium dioxide, silica, and aluminaparticles may increase rigidity and surface hardness. Also, titaniumdioxide may be used to provide the tunable material 901 with aself-cleaning property and the Lotus effect. Further, a sacrificialmetal particle may added to the tunable material where the sacrificialmetal particle may comprise at least one metal of zinc, magnesium,nickel, aluminum, and cobalt.

Additionally, glass and basalt fibers can be metal silicates containingmainly alkali metals, earth alkali metals, and aluminum. Glass maycontain borate, while basalt fiber may contain several other metalcations. APTMS can bind with silicic acid or metal cations. The APTMSmay react slowly with ionized form of silicic acid. Thus, treating glassand basalt fiber with an acid, either gaseous or liquid, may improve thereaction time. These acids may include, but are not limited to, dilutehydrochloric, sulfuric, formic, and acetic acids. Short treatment withan acid like hydrofluoric acid or ammonium fluoride is also possible.The carbon fiber within the tunable material 801 may have oxygencontaining functionalities, such as carboxylic and hydroxylic groups,and the trimethoxysilane group of APTMS may be able to bind with thesefunctionalities.

The tunable material 901 may also comprise at least one functionalizedgraphitic material, including carbon nanotubes and graphene preparedfrom the methods described herein. The functionalized graphitic materialmay be used to reinforce thermoset resins, including but not limited toepoxy and polyurethane resins. Functionalized graphitic material, forinstance functionalized carbon nanotubes, may provide a high tensilestrength and rigidity. The improved tensile strength and rigidity mayoffset the moldable thermoset plastic 905.

Within the tunable material 901, silicone may also be added. Thesilicone within the tunable material 901 can be used to adjustelasticity within the material. The silicone within the tunable material901 may contain a siloxane structure, and it may be soft and deformable.The amount of silicone within the tunable material 901 may be adjustedto provide a durable material.

Each component of the present tunable material 901 may providefunctionality. A thermoset resin 905 may constitute greater than about90% of the total mass of the composite. The range for macroparticles902, microparticles 903, and nanoparticles 904 may be about 5% to about80%, depending of the desired hardness. The range for macroparticles902, microparticles 903, and nanoparticles 904 may also be about 10% toabout 35%. Siloxane can be as low as about 0.05% where it may act withinthe interface of the matrix and particles. When siloxane may act as acomponent of the matrix of the tunable material 901, it may range fromabout 0.1% to about 50%, depending on the desired elasticity.Functionalized graphene may be about 0.1% to about 5%. Mechanicalproperties may improve between about 0.3% and about 0.8%, but electricalconductivity may improve at about 2%. Within the tunable material 901,the composition can vary, depending upon the application andcharacteristics desired.

Within the tunable material composition described herein, titaniumdioxide nanoparticles may electronically activate oxygen molecules inlight. Activated oxygen may then be able to oxidize organic impuritieson the surface. Thus, the fabrication of self-cleaning surfaces can bepossible. However, the surface itself may be oxidized. Two methods canbe used to prevent the oxidation of the surface. The first method may beto increase the inorganic particle concentration. The second method maybe to add fluorinated compounds, such as polyfluoro carboxylic acids,alcohols, or aromatic compounds that are chemically bound, for example,with functionalized carbon nanotubes or silicone.

Particles may increase hardness and abrasion resistance of a surface.Pigments may also be used to give a certain color. For example, titaniumdioxide macroparticles and microparticles can provide a white color,despite of the presence of black functionalized carbon nanotubes.Titanium dioxide nanoparticles may also provide a self-cleaning surface.

Within the tunable material 901, there may be covalent bonding withinall of the components, including the thermoset plastic 905, siloxane,functionalized carbon nanotubes, macroparticles 902, microparticles 903,and nanoparticles 904, including silica, alumina titanium oxide, copperoxide, iron phosphate, carbon, glass, and basalt fiber if thesecomponents are present. In a tunable material 901, the components may bein close vicinity of each other, and each component may provide achemical coupling at molecular level with the neighboring component.Trimethoxysilane groups may also be able to bind glass fiber or basaltfiber when the liquid mixture of the epoxy and hardener may be broughtinto contact with those fibers, functionalizing the carbon nanotubes.This can be achieved by mixing APTMS with a diamine or polyaminehardener before the functionalization.

The surface may contain macroparticles 902 that are embedded andchemically bound with a polymer matrix. Macroparticles 902 can be sand,glass powder, basalt, silica, alumina, titanium dioxide, graphitefibers, or almost any ceramic material. Microparticles 903 may fill thevoids between macroparticles 902, and help to make the surface smoother.The surface may have both microparticle and nano scale roughness. Microscale roughness can aid in aerodynamics, and nano scale roughness maygive a hydrophobic surface or Lotus effect. Nano scale roughness can beachieved by nanoparticles 904.

Within the method described herein, the preparation of graphene or CNTmay also incorporate at least one particle of nanoparticles andmicroparticles into the carbon dispersion, and at least one particle ofnanoparticles and microparticles within the second carbon dispersion.Both nanoparticles and microparticles may help with the exfoliation ofthe graphene or CNT, and can prevent reassembly of graphene back tographite. The addition of a least one of the nanoparticles andmicroparticles may include silica, alumina, carbon nanotubes, andamorphous carbon.

FIG. 10 provides a schematic of a surface structure of an abrasion andcorrosion resistant coating 1001. The schematic in FIG. 10 may show bothmicro scale and nano scale surface roughness. This kind of structure maybe useful in certain applications such as windmill blades.Microstructure can reduce friction against water 1004 and airflow. Airmay then circulate in microsized pockets 1005, and can act like a ballbearing between solid surfaces. Nanoparticles 1003 within the coatingsurface 1002 may create a nano corrugation that reduces the interactionbetween water 1006 and the surface beneath the coating. The surfacetension of water 1006 can prevent the water from following nano scalevariations. Due to weak interaction at nano scale, water may not be ableto follow even micro scale corrugation, so that the adhesion of water1006 may be further reduced and the water 1006 may not be able topenetrate into the corrosion resistant coating 1001. Thus, water 1006can be totally removed from the coating surface 1002 as well as thecoating 1001 itself on the substrate. The removal of water 1006 may beneeded in both humid and cold environments where ice formation mayhamper the coating 1001.

The materials of the coating 1001 may include conventional epoxies andpolyurethanes. In addition, materials of the coating 1001 may becorrosion resistant as well as both chemically and physically durable.In typical coatings, corrosive liquids such as water, acids, and alkalismay seep through nanocracks can then corrode the underlying surface,potentially causing the coating to detach. This process can be reducedor prevented by the use of the present coating described herein. Thermalexpansion and contraction cycles within the coating 1001 describedherein may not cause nanocracks because carbon nanotubes within thecoating 1001 can prevent this cracking. Moreover, siloxane may help theepoxy or polyurethane to be more plastic and resist any cracking. If thecoating 1001 is used to protect a surface against water, including saltwater, additional protective layers may be needed. Carbon nanotubes andgraphene may make the coating 1001 electrically conducting, although theconcentration of carbon nanotubes and graphene CNTs and graphene may bekept so low that the resistance can be high.

Besides the tunable coating described herein, a corrosion resistantcoatings system may be provided wherein the tunable coating may beincorporated into the system. One embodiment of the method of making acorrosion resistant coating system may comprise the steps of: 1)providing a substrate; 2) applying to the substrate a first layer of atunable material composition comprising a thermoset plastic; and atleast one functionalized graphitic material of carbon nanotubes andgraphene prepared by the method comprising the steps of: providing agraphitic material; providing a first molecule comprising a first group,a spacer, and a second group; providing a second molecule comprising athird group, a spacer, and a fourth group, wherein said third group is adifferent group from said first group; and bonding the second group andthe fourth group to the graphitic material; 2) applying a second layercomprising an electrically insulating material to the first layer; and3) applying to the second layer a third layer of a tunable materialcomposition comprising a thermoset plastic; and at least onefunctionalized graphitic material of carbon nanotubes and grapheneprepared by the method comprising the steps of: providing a graphiticmaterial; providing a first molecule comprising a first group, a spacer,and a second group; providing a second molecule comprising a thirdgroup, a spacer, and a fourth group, wherein said third group is adifferent group from said first group; and bonding the second group andthe fourth group to the graphitic material. Within the process, thefirst group may comprise at least one group of hydroxyl, thiol, amino,epoxy, carboxyl, and silyl, and the second group may comprise at leastone group of amino, epoxy, hydroxyl, carboxyl, silyl, and thiol. Alsowithin the process described herein, the third group may comprise atleast one group of thiol, carboxyl, trialkoxysilyl, phosphoryl ester,crown ether, cryptand, dioxime, and N-heterocycle, and the fourth groupmay comprise at least one group of amino, epoxy, hydroxyl, carboxyl,silyl, and thiol.

Another embodiment of the method of making such a corrosion resistantcoating system may comprise the steps of: 1) providing a substrate; 2)applying to the substrate a first layer of a tunable materialcomposition comprising a thermoset plastic; silicone; and at least onefunctionalized graphitic material of carbon nanotubes and grapheneprepared by the method comprising the steps of providing a graphiticmaterial; providing a first molecule comprising a first amino group, aspacer, and a trialkoxysiloxane group; providing a second moleculecomprising a second amino group, a spacer, and a third amino group; andbonding the first amino group and the second amino to the graphiticmaterial; 3) applying a second layer comprising an electricallyinsulating material to the first layer; and 4) applying to the secondlayer a third layer of a tunable material composition comprising athermoset plastic; silicone; and at least one functionalized graphiticmaterial of carbon nanotubes and graphene prepared by the methodcomprising the steps of providing a graphitic material; providing afirst molecule comprising a first amino group, a spacer, and atrialkoxysiloxane group; providing a second molecule comprising a secondamino group, a spacer, and a third amino group; and bonding the firstamino group and the second amino to the graphitic material.Alternatively, the method of making such a corrosion resistant coatingsystem may comprise the steps of: 1) providing a substrate; 2) applyingto the substrate a first layer of a tunable material compositioncomprising a thermoset plastic; silicone; and at least onefunctionalized graphitic material of carbon nanotubes and grapheneprepared by the method comprising the steps of providing a graphiticmaterial; providing a first molecule comprising a second amino group, aspacer, and a third amino group; providing a second molecule comprisinga first amino group, a spacer, and a trialkoxysiloxane group; andbonding the first amino group and the second amino to the graphiticmaterial; 3) applying a second layer comprising an electricallyinsulating material to the first layer; and 4) applying to the secondlayer a third layer of a tunable material composition comprising athermoset plastic; silicone; and at least one functionalized graphiticmaterial of carbon nanotubes and graphene prepared by the methodcomprising the steps of providing a graphitic material; providing afirst molecule comprising a second amino group, a spacer, and a thirdamino group; providing a second molecule comprising a first amino group,a spacer, and a trialkoxysiloxane group; and bonding the first aminogroup and the second amino to the graphitic material. Within thefunctionalized graphitic material of carbon nanotubes and grapheneprepared by the methods described herein, the molecule comprising anamino group, a spacer, and a trialkoxysiloxane group may be addedsimultaneously with the molecule comprising an amino group, a spacer,and an additional amino group. Also, combinations of the above methodsmay also be used.

The primer (undercoat first layer) cannot sacrifice the physicalintegrity of the coating. The undercoat first layer may comprise a firsttunable material composition. The primer may also contain at least onesacrificial metal particle of magnesium, zinc, nickel, and cobalt. Thisundercoat first layer may provide galvanic protection against corrosion.The middle layer, or second layer, may be electrically insulating andcan contain reinforcements including but not limited to at least onereinforcing material of silicon carbide whiskers, aluminum oxide fibersor tubes, hydrogenated graphene, hydrogenated nanotubes, and carbonnanotubes. The top coat, or third layer, may contain at least onegraphitic material of carbon nanotubes and graphene that may befunctionalized within the second tunable material composition. The topcoat, or third layer, may also contain an optionally biocidic compoundas well as particles that may make the coating self-healing andcorrosion resistant. The top coat, or third layer, may or may not beidentical to the undercoat first layer comprising the first tunablematerial composition.

The present coating described in FIGS. 9 and 10 and herein may be usedin, but may not be limited to, applications with vehicles, boats, ships,oil and gas pipes, and windmill blades. The tunable material compositionis used in anticorrosive coatings in electromagnetic interferenceshields, magnetic shields, conductors, super capacitors, pre-impregnatedcomposites.

The following examples illustrate the present methods in a way that itcan be practiced, but as such these examples should not be interpretedas limitations upon the overall scope of the methods described herein.

Example 1

Multiwalled CNTs (10 g, Baytubes, Bayer, Germany) and 10 g ofaminopropyl trimethoxysilane were sonicated in 1000 g Jeffamine ED-900hardener (Huntsman, USA) using 1 g aluminum tripropoxide as catalyst.Power was 800 W and the time was about 10 min. This hardener, denoted asHNT-hardener, was ready to be used with bisphenol A epoxy that contained80 ml of dimethyl dimethoxysilane and 20 g of diphenyl dimethoxysilane.

Example 2

Multiwalled CNTs (10 g, Baytubes, Bayer, Germany), 5 g of silica and 5 gof alumina nanoparticles, and 10 g of aminopropyl trimethoxysilane wereground about 30 minutes in mortar in 100 ml Jeffamine ED-900 hardener(Huntsman, USA). This hardener was diluted to 1000 g with neat JeffamineHK-511, and denoted as HNT-NP-hardener, was ready to be used with 1450 gof bisphenol A epoxy that contained 80 ml of dimethyl dimethoxysilaneand 20 g of diphenyl dimethoxysilane.

Example 3

The material of Example 2 was diluted with 200 ml of isopropanol,filtered, and washed with 100 ml of isopropanol. The solid was driedunder vacuum. Functionalized CNTs were dispersed into 1000 ml of3,3′-dimethyl-4,4′-diaminodicyclohexylmethane.

Example 4

Into 1 kg of bisphenol A diglycidyl ether, 10 g of graphite powder (200mesh, Alfa Aesar) was added using mechanical mixing. The mixture wasdegassed in a bath sonicator under nitrogen. The crude graphitedispersion was processed with LV1 Microfluidizer Processor IDEX MaterialProcessing Technologies Group) three times using 1500000 mmHg (2500 bar)pressure.

Example 5

The product from Example 3 was mixed with 100 g of zinc powder in aclosed metal can using roller mixer. The coated zinc powder was furthermixed with high speed mechanical mixer with Epon 828. Melamine curingagent was added, and six test plates were coated with 20 micrometerlayer of this coating material. Polyurethane topcoat was applied ontothese plates. Six reference plates were similarly coated with acomposition that contained the same components, but CNTs were usedinstead of the amino-trimethoxysilane-CNT. The plates were tested insalt-fog chamber 1000 hours. Rust was measured colorimetrically. Theplates that were coated with this method had about 24±11% less rustformation.

The implementations have been described, hereinabove. It will beapparent to those skilled in the art that the above methods andapparatuses may incorporate changes and modifications without departingfrom the general scope of these methods. It is intended to include allsuch modifications and alterations in so far as they come within thescope of the appended claims or the equivalents thereof.

What is claimed is:
 1. A corrosion resistant material comprising: asubstrate; a first material comprising: less than about 90% of an aminogroup or epoxy group; between about 0.05% and about 50% siloxane;between about 5% and about 80% nanoparticles, microparticles, ormacroparticles; and between about 0.1% and about 5% of a firstfunctionalized graphitic material, wherein the first functionalizedgraphitic material comprises: a sacrificial metal particle selected fromthe group consisting of magnesium, aluminum, zinc, nickel, cobalt, andcombinations thereof; a first molecule chemically bound to the firstfunctionalized graphitic material, the first molecule comprising a firstgroup, a first spacer, and a second group, wherein the first groupcomprises at least one of hydroxyl, thiol, amino, epoxy, carboxyl, andsilyl, wherein the second group comprises at least one of amino, epoxy,hydroxyl, carboxyl, silyl, and thiol; a second molecule chemically boundto the first functionalized graphitic material, the second moleculecomprising a third group, a second spacer, and a fourth group, whereinthe third group is a different group from the first group, wherein thethird group comprises at least one of thiol, carboxyl, trialkoxysilyl,phosphoryl ester, crown ether, cryptand, dioxime, and N-heterocycle,wherein the fourth group comprises at least one of amino, epoxy,hydroxyl, carboxyl, silyl, and thiol, wherein the sacrificial metalparticle is bound to either the first group or the third group, whereineither the first group or the third group is bound to the substrate,wherein the group bound to the substrate is different from the groupbound to the sacrificial metal particle, wherein the second group andthe fourth group are chemically bound to the first functionalizedgraphitic material; a second material comprising: less than about 90% ofa silyl group; between about 0.05% and about 50% siloxane; between about5% and about 80% nanoparticles, microparticles, or macroparticles; andbetween about 0.1% and about 5% of a second functionalized graphiticmaterial; a third material comprising: less than about 90% of an aminogroup or epoxy group and a silyl group; between about 0.05% and about50% siloxane; between about 5% and about 80% nanoparticles,microparticles, or macroparticles; and between about 0.1% and about 5%of a third functionalized graphitic material; a monomer of a thermosetpolymer chemically bound to the amino or epoxy group of the firstmaterial, the second material, and the third material; and a monomer ofan elastic polymer to chemically bound to the silyl group of the firstmaterial, the second material, and the third material, wherein the firstmaterial, the second material, and the third material are attached tothe substrate.
 2. The material of claim 1, wherein the secondfunctionalized graphitic material comprises: a sacrificial metalparticle selected from the group consisting of magnesium, aluminum,zinc, nickel, cobalt, and combinations thereof; a first moleculechemically bound to the second functionalized graphitic material, thefirst molecule comprising a first group, a first spacer, and a secondgroup, wherein the first group comprises at least one of hydroxyl,thiol, amino, epoxy, carboxyl, and silyl, wherein the second groupcomprises at least one of amino, epoxy, hydroxyl, carboxyl, silyl, andthiol; and a second molecule bound to the second functionalizedgraphitic material, the second molecule comprising a third group, asecond spacer, and a fourth group, wherein the third group is adifferent group from the first group, wherein the third group comprisesat least one of thiol, carboxyl, trialkoxysilyl, phosphoryl ester, crownether, cryptand, dioxime, and N-heterocycle, wherein the fourth groupcomprises at least one of amino, epoxy, hydroxyl, carboxyl, silyl, andthiol, wherein the sacrificial metal particle is bound to either thefirst or the third group, wherein either the first or the third group isbound to the substrate, wherein the group bound to the substrate isdifferent from the group bound to the sacrificial metal particle,wherein the second group and the fourth group is chemically bound to thesecond functionalized graphitic material.
 3. The material of claim 2,wherein the first functionalized graphitic material further comprises:thermoset resin side chains on the first functionalized graphiticmaterial; and elastomer side chains on the first functionalizedgraphitic material.
 4. The material of claim 3, wherein the thirdfunctionalized graphitic material comprises: a sacrificial metalparticle selected from the group consisting of magnesium, aluminum,zinc, nickel, cobalt, and combinations thereof; a first moleculechemically bound to the third functionalized graphitic material, thefirst molecule comprising a first group, a first spacer, and a secondgroup, wherein the first group comprises at least one of hydroxyl,thiol, amino, epoxy, carboxyl, and silyl, wherein the second groupcomprises at least one of amino, epoxy, hydroxyl, carboxyl, silyl, andthiol; and a second molecule chemically bound to the thirdfunctionalized graphitic material, the second molecule comprising athird group, a second spacer, and a fourth group, wherein the thirdgroup is a different group from the first group, wherein the third groupcomprises at least one of thiol, carboxyl, trialkoxysilyl, phosphorylester, crown ether, cryptand, dioxime, and N-heterocycle, wherein thefourth group comprises at least one of amino, epoxy, hydroxyl, carboxyl,silyl, and thiol, wherein the sacrificial metal particle is bound toeither the first or the third group, wherein either the first or thethird group is bound to the substrate, wherein the group bound to thesubstrate is different from the group bound to the sacrificial metalparticle, wherein the second group and the fourth group is chemicallybound to the third functionalized graphitic material.
 5. The material ofclaim 4, wherein the second functionalized graphitic material furthercomprises: thermoset resin side chains on the second functionalizedgraphitic material; and elastomer side chains on the secondfunctionalized graphitic material.
 6. The material of claim 5, whereinthe third functionalized graphitic material further comprises: thermosetresin side chains on the third functionalized graphitic material; andelastomer side chains on the third functionalized graphitic material. 7.The material of claim 3, wherein the elastomer side chain is siloxane.8. The material of claim 5, wherein the elastomer side chain issiloxane.
 9. The material of claim 6, wherein the elastomer side chainis siloxane.
 10. The material of claim 1, wherein the firstfunctionalized graphitic material, the second functionalized graphiticmaterial, and the third functionalized graphitic material are carbonnanotubes or graphene.
 11. The material of claim 10, wherein the firstfunctionalized graphitic material, the second functionalized graphiticmaterial, and the third functionalized graphitic material are graphene.12. The material of claim 1, wherein the first spacer and the secondspacers of the first functionalized graphitic material have a length ofless than about 1 nm.
 13. The material of claim 2, wherein the firstspacer and the second spacers of the second functionalized graphiticmaterial have a length of less than about 1 nm.
 14. The material ofclaim 4, wherein the first spacer and the second spacers of the thirdfunctionalized graphitic material have a length of less than about 1 nm.15. The material of claim 1, wherein the first spacer and the secondspacers of the first functionalized graphitic material containaliphatic, aromatic or heterocyclic moieties.
 16. The material of claim2, wherein the first spacer and the second spacers of the secondfunctionalized graphitic material contain aliphatic, aromatic orheterocyclic moieties.
 17. The material of claim 4, wherein the firstspacer and the second spacers of the third functionalized graphiticmaterial contain aliphatic, aromatic or heterocyclic moieties.
 18. Thematerial of claim 1, wherein the macroparticles are at least onemacroparticle chosen from the group consisting of sand, glass, basalt,alumina, silica, titanium dioxide, ceramic, and graphite fibers.
 19. Thematerial of claim 1, wherein the microparticles are at least onemicroparticle chosen from the group consisting of titanium dioxide,silica, ceramic, graphite, iron phosphate, alumina, nickel, cobalt,zinc, aluminum, and magnesium.
 20. The material of claim 1, wherein thenanoparticles are at least one nanoparticle chosen from the groupconsisting of titanium dioxide, copper oxide, iron phosphate, silver,silica, and alumina.